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San Diego based Grolltex was granted a patent by the USPTO for a new multi-modal ‘super’ sensor design made of single layer graphene.

The patent, titled “Graphene-based multi-modal sensor” describes a one atom thick architecture and utilizes several of Grolltex’ 2D materials technologies to produce what the company internally calls ‘The smallest, most sensitive sensor in the world’.

The company is working on initial applications for these sensors that are targeting the bio-sensing and defense fields as leading-edge users of this technology.

“Our single atom thick sensor design, in the strain sensor configuration, is so sensitive that it captures a robust and repeatable signal on the contractility strength of individual ‘cardio myocytes’ or heart cells as they beat”, said Jeff Draa, company co-founder and CEO.

“This can be a holy grail for fields such as cardiotoxicity testing as it has the capacity to be a significant time and money saver in the new drug testing and approval process”.

Additionally, the single layer graphene sensor covered by this patent has a very high threshold for thermal coefficient of resistance, meaning it experiences little to no signal drift when exposed to extreme levels of heat. This makes it an ideal sensor for measuring micro strain in high speed aeronautical vehicles.

These sensors are so small and thin, they can be layered into the skins of airplanes, helicopters or other high stress vehicles to real-time measure and detect micro stress at architectures and levels not currently possible with today’s sensing technologies. These sensors could also be discreetly placed within critical structures such as bridges or buildings.

An illustration of the molecular structure of graphene nanoribbons produced by UCLA scientists. Credit: Yves Rubin

Silicon—the shiny, brittle metal commonly used to make semiconductors—is an essential ingredient of modern-day electronics. But as electronic devices have become smaller and smaller, creating tiny silicon components that fit inside them has become more challenging and more expensive.

Now, UCLA chemists have developed a new method to produce nanoribbons of graphene, next-generation structures that many scientists believe will one day power electronic devices.

This research is published online in the Journal of the American Chemical Society.

The nanoribbons are extremely narrow strips of graphene, the width of just a few carbon atoms. They’re useful because they possess a bandgap, which means that electrons must be “pushed” to flow through them to create electrical current, said Yves Rubin, a professor of chemistry in the UCLA College and the lead author of the research.

“A material that has no bandgap lets electrons flow through unhindered and cannot be used to build logic circuits,” he said.

Rubin and his research team constructed graphene nanoribbons molecule by molecule using a simple reaction based on ultraviolet light and exposure to 600-degree heat.

“Nobody else has been able to do that, but it will be important if one wants to build these molecules on an industrial scale,” said Rubin, who also is a member of the California NanoSystems Institute at UCLA.

The process improves upon other existing methods for creating graphene nanoribbons, one of which involves snipping open tubes of graphene known as carbon nanotubes. That particular approach is imprecise and produces ribbons of inconsistent sizes—a problem because the value of a nanoribbon’s bandgap depends on its width, Rubin said.

To create the nanoribbons, the scientists started by growing crystals of four different colorless molecules. The crystals locked the molecules into the perfect orientation to react, and the team then used light to stitch the molecules into polymers, which are large structures made of repeating units of carbon and hydrogen atoms.

The scientists then placed the shiny, deep blue polymers in an oven containing only argon gas and heated them to 600 degrees Celsius. The heat provided the necessary boost of energy for the polymers to form the final bonds that gave the nanoribbons their final shape: hexagonal rings composed of carbon atoms, and hydrogen atoms along the edges of the ribbons.

“We’re essentially charring the polymers, but we’re doing it in a controlled way,” Rubin said.

The process, which took about an hour, yielded graphene nanoribbons just eight carbon atoms wide but thousands of atoms long. The scientists verified the molecular structure of the nanoribbons, which were deep black in color and lustrous, by shining light of different wavelengths at them.

“We looked at what wavelengths of light were absorbed,” Rubin said. “This reveals signatures of the structure and composition of the ribbons.”

The researchers have filed a patent application for the process.

Rubin said the team now is studying how to better manipulate the nanoribbons—a challenge because they tend to stick together.

“Right now, they are bundles of fibers,” Rubin said. “The next step will be able to handle each nanoribbon one by one.”

Graphene’s unique combination of electrical and physical properties marks it out as a potential candidate for transparent, stretchable electronics, which could enable a new generation of sophisticated displays, wearable health monitors, or soft robotic devices. But, although graphene is atomically thin, highly transparent, conductive, and more stretchable than conventional indium tin oxide electrodes, it still tends to crack at small strains.

“To enable excellent strain-dependent performance of transparent graphene conductors, we created graphene nanoscrolls in between stacked graphene layers,” explains first author of the study, Nan Liu

Illustration of the stacked graphene MGG structure.

The team led by Zhenan Bao dub their combination of rolled up sheets of graphene sandwiched in between stacked graphene layers ‘multi-layer G/G scrolls’ or MGG. The scrolls, which are 1–20 microns long, 0.1–1 microns wide, and 10–100 nm high, form naturally during the wet transfer process as graphene is moved from one substrate to another.

The all-carbon devices fabricated by the team retain 60% of their original current output when stretched to 120% strain (parallel to the direction of charge transport). This is the most stretchable carbon-based transistor reported to date, believe the researchers.

The graphene scrolls are key to the stretchable electrode’s remarkable properties because they seem to provide a conductive path even when graphene sheets start to crack at high strain levels.

“Taking into account the electronic and optical properties as well as the cost, our MGG exhibits substantial strengths over other conductors, such as carbon nanotubes and metal nanowires,” says Liu.

Transparent, stretchable graphene electrodes could be useful as contacts in flexible electronic circuits such as backplane control units for displays, as well as functional sensors and digital circuits for electronic skin.

“This is a very important area of research with a variety of possible applications,” comments Andrea C. Ferrari of the University of Cambridge. “The approach taken by Bao et al. is an interesting one that could be quite general.”

The concept of using a mixture of graphene scrolls and platelets to enable an electrode to stretch without significant losses in transmittance or conductivity is a good and should, in principle, not be too complicated to scale up for real devices, he adds.

“We are now seeking to extend this method to other two-dimensional materials, such as MoS2, to enable stretchable two-dimensional semiconductors,” says Liu.

Researchers of the ICN2 Theoretical and Computational Nanoscience Group, led by ICREA Prof. Stephan Roche, have published another paper on spin, this time reporting numerical simulations for spin relaxation in graphene/TMDC heterostructures.

Published in Physical Review Letters this week, spintronics researchers of the ICN2 Theoretical and Computational Nanoscience Group led by ICREA Prof. Stephan Roche have gleaned potentially game-changing insight into the mechanisms governing spin dynamics and relaxation in graphene/TMDC heterostructures. Not only do their models give a spin lifetime anisotropy that is orders of magnitude larger than the 1:1 ratio typically observed in 2D systems, but they point to a qualitatively new regime of spin relaxation.

Spin relaxation is the process whereby the spins in a spin current lose their orientation, reverting to a natural disordered state. This causes spin signal to be lost, since spins are only useful for transporting information when they are oriented in a certain direction.

This study reveals that the rate at which spins relax in graphene/TMDC systems depends strongly on whether they are pointing in or out of the graphene plane, with out-of-plane spins lasting tens or hundreds of times longer than in-plane spins. Such a high ratio has not previously been observed in graphene or any other 2D material.

In the paper, aptly titled “Giant Spin Lifetime Anisotropy in Graphene Induced by Proximity Effects”, lead author Aron Cummings reports that this behaviour is mediated by the spin-valley locking induced in graphene by the TMDC, which ties the lifetime of in-plane spin to the intervalley scattering time. This causes in-plane spin to relax much faster than out-of-plane spin.

Furthermore, the numerical simulations suggest that this mechanism should come into play in any substrate with strong spin-valley locking, including the TMDCs themselves.

Effectively inducing a spin filter effect –the ability to sort or tweak spin orientations–, these findings give reason to believe that it might one day be possible to manipulate, and not just transport, spin in graphene.

These simulations have since been borne out experimentally by colleagues in the ICN2 Physics and Engineering of Nanodevices Group, led by ICREA Prof. Sergio Valenzuela. Paper coming soon.

Background:

Spintronics is a branch of electronics that uses the spin of subatomic particles like electrons to store and transport information. It promises devices that are faster, operate at a fraction of the energy cost and have vastly superior memories. However, establishing a spin current is not a straightforward process. First, because spin in its natural state is disordered; that is, the spin axes are pointing in any number of directions. They must first be polarised to tune their orientation.

Then, even once polarised, the spins can lose this orientation easily in a process known as spin relaxation, which limits the lifetime and therefore usefulness of spin currents in practice.

Enter graphene, very much the material of the moment and not without good reason: this 2D material boasts a series of properties that make it uniquely suited for maintaining spin orientation over long lifetimes. However, its low spin-orbit coupling (SOC) makes it ineffective for manipulating spin.

The solution adopted in spintronics is to create layered heterostructures, harnessing the spin transport properties of graphene and a second high SOC material in a single system. This works through the proximity effect, whereby graphene becomes imprinted with the properties of the second material, and has been proven experimentally with 2D magnetic insulators and transition metal dichalcogenides (TMDCs).

In this work, researchers have studied spin relaxation in such layered graphene/TMDC heterostructures in a bid to shed some light on the as yet unexplored mechanisms governing spin relaxation in these systems. Spin lifetime anisotropy is the ratio of out-of-plane to in-plane spin lifetimes, and is used as a measurement of these mechanisms. What they find is a unique mechanism enabled by the specific proximity effect of TMDCs on graphene.

The University of Minnesota team produced a microchip containing a large array of graphene electronic tweezers. Fluorescence images show DNA molecules and polystyrene nanoparticles trapped on the chip. Credit: Barik et al., University of Minnesota

Researchers from the University of Minnesota College of Science and Engineering have found yet another remarkable use for the wonder material graphene—tiny electronic “tweezers” that can grab biomolecules floating in water with incredible efficiency. This capability could lead to a revolutionary handheld disease diagnostic system that could be run on a smart phone.

Graphene, a material made of a single layer of carbon atoms, was discovered more than a decade ago and has enthralled researchers with its range of amazing properties that have found uses in many new applications from microelectronics to solar cells.

The graphene tweezers developed at the University of Minnesota are vastly more effective at trapping particles compared to other techniques used in the past due to the fact that graphene is a single atom thick, less than 1 billionth of a meter.

The research study was published today in Nature Communications, a leading journal in the field of nanomaterials and devices.

The world’s sharpest tweezers

The physical principle of tweezing or trapping nanometer-scale objects, known as dielectrophoresis, has been known for a long time and is typically practiced by using a pair of metal electrodes. From the viewpoint of grabbing molecules, however, metal electrodes are very blunt. They simply lack the “sharpness” to pick up and control nanometer-scale objects.

“Graphene is the thinnest material ever discovered, and it is this property that allows us to make these tweezers so efficient. No other material can come close,” said research team leader Sang-Hyun Oh, a Sanford P. Bordeau Professor in the University of Minnesota’s Department of Electrical and Computer Engineering. “To build efficient electronic tweezers to grab biomolecules, basically we need to create miniaturized lightning rods and concentrate huge amount of electrical flux on the sharp tip. The edges of graphene are the sharpest lightning rods.”

The team also showed that the graphene tweezers could be used for a wide range of physical and biological applications by trapping semiconductor nanocrystals, nanodiamond particles, and even DNA molecules. Normally this type of trapping would require high voltages, restricting it to a laboratory environment, but graphene tweezers can trap small DNA molecules at around 1 Volt, meaning that this could work on portable devices such as mobile phones.

Using the University of Minnesota’s state-of-the-art nanofabrication facilities at the Minnesota Nano Center, electrical and computer engineering Professor Steven Koester’s team made the graphene tweezers by creating a sandwich structure where a thin insulating material call hafnium dioxide is sandwiched between a metal electrode on one side and graphene on the other. Hafnium dioxide is a material that is commonly used in today’s advanced microchips.

Atomically sharp edges of electrically driven graphene can act as ‘tweezers’ that rapidly trap biomolecules from the surrounding solution. Credit: In-Ho Lee, University of Minnesota

“One of the great things about graphene is it is compatible with standard processing tools in the semiconductor industry, which will make it much easier to commercialize these devices in the future,” said Koester, who led the effort to fabricate the graphene devices.

“Since we are the first to demonstrate such low-power trapping of biomolecules using graphene tweezers, more work still needs to be done to determine the theoretical limits for a fully optimized device,” said Avijit Barik, a University of Minnesota electrical and computer engineering graduate student and lead author of the study. “For this initial demonstration, we have used sophisticated laboratory tools such as a fluorescence microscope and electronic instruments. Our ultimate goal is to miniaturize the entire apparatus into a single microchip that is operated by a mobile phone.”

Tweezers that can ‘feel’

Another exciting prospect for this technology that separates graphene tweezers from metal-based devices is that graphene can also “feel” the trapped biomolecules. In other words, the tweezers can be used as biosensors with exquisite sensitivity that can be displayed using simple electronic techniques.

“Graphene is an extremely versatile material,” Koester said. “It makes great transistors and photodetectors, and has the potential for light emission and other novel biosensor devices. By adding the capability to rapidly grab and sense molecules on graphene, we can design an ideal low-power electronics platform for a new type of handheld biosensor.”

Oh agrees that the possibilities are endless.

“Besides graphene, we can utilize a large variety of other two-dimensional materials to build atomically sharp tweezers combined with unusual optical or electronic properties,” said Oh. “It is really exciting to think of atomically sharp tweezers that can be used to trap, sense, and release biomolecules electronically. This could have huge potential for point-of-care diagnostics, which is our ultimate goal for this powerful device.”

In addition to Oh, Koester, and Barik, other researchers on the team include University of Minnesota Department of Electrical and Computer Engineering Assistant Professor Tony Low, graduate student Yao Zhang, and postdoctoral researcher Roberto Grassi, as well as Professor Joshua Edel and research associate Binoy Paulose Nadappuram from Imperial College London.

The University of Minnesota research was funded primarily by the National Science Foundation and the Minnesota Partnership for Biotechnology and Medical Genomics, a unique collaborative venture among the University of Minnesota, Mayo Clinic, and the State of Minnesota.

Previously graphene-oxide membranes were shown to be completely impermeable to all solvents except for water. However, a study published in Nature Materials, now shows that we can tailor the molecules that pass through these membranes by simply making them ultrathin.

The research team led by Professor Rahul Nair at the National Graphene Institute and School of Chemical Engineering and Analytical Science at The University of Manchester tailored this membrane to allow all solvents to pass through but without compromising it’s ability to sieve out the smallest of particles.

In the newly developed ultrathin membranes, graphene-oxide sheets are assembled in such a way that pinholes formed during the assembly are interconnected by graphene nanochannels, which produces an atomic-scale sieve allowing the large flow of solvents through the membrane.

This new research allows for expansion in the applications of graphene based membranes from sea water desalination to organic solvent nanofiltration (OSN). Unlike sea water desalination, which separate salts from water, OSN technology separates charged or uncharged organic compounds from an organic solvent.

As an example, Manchester scientists demonstrated that graphene-oxide membranes can be designed to completely remove various organic dyes as small as a nanometre dissolved in methanol.

Credit: University of Manchester

Prof. Nair said, “Just for a fun, we even filtered whisky and cognac through the graphene-oxide membrane. The membrane allowed the alcohol to pass through but removed the larger molecules, which gives the amber colour. The clear whisky smells similar to the original whisky but we are not allowed to drink it in the lab, however it was a funny Friday night experiment!”

The newly developed membranes not only filter out small molecules but it boosts the filtration efficiency by increasing the solvent flow rate.

Prof. Nair added “Chemical separation is all about energy, various chemical separation processes consume about half of industrial energy useage. Any new efficient separation process will minimize the consumption of energy, which is in high demand now. By 2030, the world is projected to consume 60% more energy than today.”

Dr. Su, who led the experiment added “The developed membranes are not only useful for filtering alcohol, but the precise sieve size and high flux open new opportunity to separate molecules from different organic solvents for chemical and pharmaceutical industries. This development is particularly important because most of the existing polymer-based membranes are unstable in organic solvents whereas the developed graphene-oxide membrane is highly stable.”

How Can Graphene Help Desalination?

Graphene-oxide membranes developed at the National Graphene Institute have attracted widespread attention for water filtration and desalination applications, providing a potential solution to the water scarcity.

By using ultra-thin membranes, this is the first clear-cut experiment to show how other solvents can be filtered out, proving that there is potential for organic solvent nanofiltration.

Graphene- the world’s first two-dimensional material is known for its versatile superlatives, it can be both hydrophobic and hydrophilic, stronger than steel, flexible, bendable and one million times thinner than a human hair.

This research has changed the perception of what graphene-oxide membranes are capable of and how we can use them. By being able to design these membranes to filter specific molecules or solvents, it opens up new potential uses that have previously not been explored.

Researchers in Canada have developed a technique for improving the energy storage capacity of supercapacitors. These developments could allow for mobile phones to eventually charge in seconds.

A supercapacitor can store far more electrical energy than a standard capacitor. They are able to charge and discharge far more rapidly than batteries, making them a much-discussed alternative to traditional batteries.

The main drawback of supercapacitors as a replacement for batteries is their limited storage: while they can store 10 to 100 times more electrical energy than a standard capacitor, this is still not enough to be useful as a battery replacement in smartphones, laptops, electric vehicles and other machines.

At present, supercapacitors can store enough energy to power laptops and other small devices for approximately a tenth as long as rechargeable batteries do.

Increases in the storage capacity of supercapacitors could allow for them to be made smaller and lighter, such that they can replace batteries in some devices that require fast charging and discharging.

A team of engineers at the University of Waterloo were able to create a new supercapacitor design which approximately doubles the amount of electrical energy that it can hold.

They did this by coating graphene with an oily liquid salt in the electrodes of supercapacitors. By adding a mixture of detergent and water, the droplets of the liquid salt were reduced to nanoscale sizes.

This salt acts as an electrolyte (which is required for storage of electrical charge), as well as preventing the atom-thick graphene sheets sticking together, hugely increasing their exposed surface area and optimising energy storage capacity.

“We’re showing record numbers for the energy-storage capacity of supercapacitors,” said Professor Michael Pope, a chemical engineer at the University of Waterloo. “And the more energy-dense we can make them, the more batteries we can start displacing.”

According to Professor Pope, supercapacitors could be a green replacement for lead-acid batteries in vehicles, capturing the energy otherwise wasted by buses and high-speed trains during braking. In the longer term, they could be used to power mobile phones and other consumer technology, as well as devices in remote locations, such as in orbit around Earth.

“If they are marketed in the correct ways for the right applications, we’ll start seeing more and more of them in our everyday lives,” said Professor Pope.

James Baker, Business Director for Graphene at The University of Manchester, talks to AZoNano about the current state of the graphene market and the key next steps needed.

When we last spoke back in 2015 the National Graphene Institute (NGI) had been focused on the successful commercialisation of graphene through collaborative work between research and industry. How has the graphene community developed since then?

The University of Manchester (UoM) now has over 250 researchers working on graphene and 2D materials and the National Graphene Institute (NGI) has now been open for over 2 years. The NGI has provided a key facility and capability in bringing together the multi-disciplinary research from across the University together with developing partnerships and collaborations with industry to accelerate the development of graphene products and applications.

We are also close to opening our second graphene building, the Graphene Engineering Innovation Centre, next year. This will allow the University to create a unique hub for 2D materials knowledge and commercialisation in Manchester alongside close links with industry.

The graphene roadmap was a crucial part of the conversation two years ago. Where do you think the industry currently stands in-line with these predictions?

Road-mapping is a key part of the commercialisation journey but I am now seeing a much more significant “applications pull” from industry which is resulting in increasing engagement of activity and translation into projects and the development of new graphene enhanced concepts and applications.

You recently spoke about commercialisation at Graphene Week 2017. What were the key areas of discussion this year?

As always there is a significant amount of new science being presented at Graphene Week, but there was also evidence of industry now starting to get “interesting” and “beneficial” results from their engagements and projects involving graphene with a significant amount of progress having taken place over the past two years.

A common challenge when attempting to make a graphene-based sensor is the high levels of electronic noise that are caused, reducing its effectiveness. In a recent work, an international team of researchers proposed a graphene-based semiconductor device that reduces electronic noise when its electric charge is neutral (referred to as its neutrality point). The group achieved this neutrality point without the need for bulky magnetic equipment that had previously prevented these approaches from being used in portable sensor applications.

In a proof-of-concept device, the researchers used their new sensing scheme to detect HIV-related DNA hybridization at picomolar concentrations. The team fabricated a charge detector out of graphene that can detect very small amounts of charges close to its surface. The sensing principle of the device relies on charge species detection through the field-effect, which brings about a change in electrical conductance of graphene upon adsorption of a charged molecule on the sensor surface.

“Graphene is perfect for such application,” explained members of the team. “Graphene is unique among other solid-state materials in that all carbon atoms are located on the surface, making the graphene surface highly sensitive for detection of changes in the environment.”

However, the team notes that the ability to create practical electrochemically gated graphene-based field-effect transistors to detect charged species also requires a small amount of electronic noise, the existence of which fundamentally limits a sensor’s resolution.

“I believe we have discovered an elegant and simple approach to improve the sensitivity of next generation graphene electronic biochemical sensor devices,” said the team. “Our device is able to function at its low-noise neutrality point without the need for complicated magnetic equipment that other approaches using graphene have depended upon.”

The researchers add that electronic noise can be reduced without compromising the sensing response, enabling significant improvement to the signal-to-noise ratio compared to that of a conventionally operated graphene transistor to measure conductance. This noise reduction and maintaining of the sensing response is achieved by making use of one of the unique properties of graphene field-effect transistors: its ambipolar (being both n- or p-type) behavior near the neutrality point.

This neutrality point appears in graphene as the lowest point of conductance in the material and is the result of graphene’s unique electronic band structure. At this low conductance point, the graphene sensors can operate at a lower noise level. While this doesn’t compromise the sensing response, it does lower the signal-to-noise ratio of the device, resulting in an overall improved sensing response.

Another feature of the latest device is the use of so-called in-situ ‘electrochemical cleaning’ to ensure a clean graphene surface, which is a new technique meant to enable graphene electronic biosensors to provide reliable performance.
While they were able to test their sensing scheme on HIV, more work must be done before this device could find its way into the next generation of biochemical sensors.

First of all, the team believes that there is a need to scale up the miniaturized graphene electronic arrays. In addition, microfluidic or nanofludic liquid handling should also be integrated into the arrays.

There will also be a need for on-site electrochemical cleaning on each of the devices and the more surface functionalization to suit different cases of biomolecule detection.

The researchers intend to adopt this low-noise technology for other single molecule detection methods and evaluate the sensor performances when scaled up.

Lithium-ion batteries are used to power many things from mobile phones, laptops, tablets to electric cars. But they have some drawbacks, including limited energy storage capacity, low durability and long charging time.

Now, researchers at the Institute of Bioengineering and Nanotechnology (IBN) at Singapore’s Agency for Science, Technology and Research (A*STAR) have developed a way of producing more durable and longer lasting lithium-ion batteries. This finding was reported in Advanced Materials. Led by IBN Executive Director Professor Jackie Y. Ying, the researchers invented a generalized method of producing anode materials for lithium-ion batteries. The anodes are made from metal oxide nanosheets, which are ultrathin, two-dimensional materials with excellent electrochemical and mechanical properties.

These nanosheets are 50,000 times thinner than a sheet of paper, allowing faster charging of power compared to current battery technology. The wide surface area of the nanosheets makes better contact with the electrolyte, thus increasing the storage capacity. The material used is also highly durable and does not break easily, which improves the battery shelf life. Existing methods of making metal oxide nanosheets are time-consuming and difficult to scale up.

The IBN researchers came up with a simpler and faster way to synthesize metal oxide nanosheets using graphene oxide. Graphene oxide is a 2D carbon material with chemical reactivity that facilities the growth of metal oxides on its surface. Graphene oxide was used as the template to grow metal oxides into nanosheet structures via a simple mixing process, followed by heat treatment. The researchers were able to synthesize a wide variety of metal oxides as nanosheets, with control over the composition and properties. The new technique produces the nanosheets in one day, compared to one week for previously reported methods.

It does not require the use of a pressure chamber and involves only two steps in the synthesis process, making the nanosheets easy to manufacture on a large scale. Tests showed that the nanosheets produced using this generalized approach have excellent lithium-ion battery anode performance, with some materials lasting three times longer than graphite anodes used in current batteries. “Our nanosheets have shown great promise for use as lithium-ion anodes.

This new method could be the next step toward the development of metal oxide nanosheets for high performance lithium-ion batteries. It can also be used to advance other applications in energy storage, catalysis and sensors,” said Ying.

The article can be found at: AbdelHamid et al. (2017) Generalized Synthesis of Metal Oxide Nanosheets and Their Application as Li-Ion Battery Anodes. ——— Source: A*STAR.